vvEPA
United States
Environmental Protection
Agency
Environmental Sciences Research
Laboratory
Research Triangle Park NC 27711
EPA-600/3-79-097
September 1979
Research and Development
Aerosol Source
Characterization
Study in
Miami, Florida
Microscopical
Analysis
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EPA-600/3-79-097
September 1979
AEROSOL SOURCE CHARACTERIZATION STUDY IN MIAMI, FLORIDA
Microscopical Analysis
by
Ronald G. Draftz
IIT Research Institute
Chicago, Illinois 60616
Grant R803078
Project Officer
Jack L. Durham
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 27711
' -on Agency
'- - --. :l'-'M- 167,0
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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DISCLAIMER
This report has been reviewed by the Environmental Support Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of trade
names or commercial products constitute endorsement or recommendation for use.
11
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ABSTRACT
In June of 1975 the EPA conducted an experimental program in the Miami
metropolitan area to collect atmospheric aerosol samples. The sample compo-
sitions were to be identified in order to determine the aerosol sources.
Several different sample types were taken for mass, elemental, and
compound analyses. One group of samples was collected on substrates suitable
for elemental analysis. Elemental analysis was conducted using the PIXE
(proton-induced x-ray emission) technique (Johansson et al., 1972). A
second group of samples was collected on substrates suitable for optical
and scanning electron microscopy.
The microscopical analyses, conducted by IIT Research Institute, show
the composition of Miami's TSP (total suspended particulate) to be very
similar to that of Chicago, St. Louis, and Philadelphia, with the exception
that Miami receives a significant impact from ocean spray. Mineral fragments
resuspended by traffic appear to be the primary aerosol mass contributor.
Rubber tire fragments and carbonaceous vehicle exhaust are also major TSP
contributors. These conclusions are based solely on three sampling days at
three sites and need to be confirmed by additional studies. However, it is
very likely that the aerosol types and amounts reported above remain fairly
constant throughout the year. The results of PIXE analyses done on the first
group of samples are summarized in a separate report (Hardy, 1979).
This report was submitted in fulfillment of Grant No. R803078 by IIT
Research Institute under the sponsorship of the U.S. Environmental
Protection Agency. This report covers the period June 4, 1975, to June 12,
1975, and work was completed as of August 1977.
iii
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CONTENTS
Abstract iii
Figures vi
Tables ix
Acknowledgments x
1. Recommendations 1
2. Sampling Procedures 3
3. Microscopical Sample Analysis 5
Analysis of Samples Collected June 4, 1975 5
Analysis of Samples Collected June 11, 1975 10
Analysis of Samples Collected June 12, 1975 13
4. Comparison of Microscopical and Elemental Data 14
5. Results 16
References 58
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FIGURES
Number page
1 Site M-10; Hi-vol, June 4; 163x 25
2 Site M-10; Impactor Stage 3; June 4, 163x 25
3 Site M-10; Impactor Stage 4; June 4; 163x 26
4 Same sample as Figure 3 after HC1 wash; 163x 26
5 Site M-10; Impactor Stage 7; June 4; 163x 27
6 Site M-10; Impactor Stage 0; June 4; 3000x 27
7 Site M-10; Impactor Stage 3; June 4; lOOOx 28
8 X-ray spectrum of large center particle in Figure 7 28
9 Site M-10; Impactor Stage 5; June 4; lOOOx 29
10 X-ray spectrum of deposition site on Stage 5, Figure 9 29
11 Enlargement of upper cubes in Figure 10; 3000x 30
12 X-ray spectrum of cubes in Figure 11 30
13 Enlargement of lower left cubes in Figure 9; 3000x 31
14 X-ray spectrum of cubes in Figure 13 31
15 Site M-10; Impactor Stage 7; June 4; 300x 32
16 Enlargement of one crystal shown in Figure 15; 3000x 32
17 X-ray spectrum of one crystal shown in Figure 15 33
18 Site M-ll; Hi-vol; June 4; 163x 33
19 Site M-ll; Impactor Stage 0; June 4; 163x 39
20 Site M-ll; Impactor Stage 3; June 4; 407x 34
21 Site M-ll; Impactor Stage 4; June 4; 163x 35
22 Site M-ll; Impactor Stage 5; June 4; 407x 35
23 Site M-ll; Impactor Stage 6; June 4; 163x 36
24 Site M-ll; Impactor Stage 7; June 4; 163x 36
25 Same sample as Figure 24 with polars crossed to show
large ammonium sulfate crystal; 163x 37
26 Site M-14; Hi-vol; June 4; 163x 37
VI
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FIGURES (continued)
Number Page
27 Same sample as Figure 26; 407x 30
28 Site M-14; Impactor Stage 0; June 4; 163x 38
29 Same sample as Figure 28 showing group of particles
recrystallized from liquid; 407x 39
30 Site M-14; Impactor Stage 1; June 4; 163x 39
31 Site M-14; Impactor Stage 2; June 4; 163x 40
32 Same sample as Figure 31; 407x 40
33 Site M-14; Impactor Stage 3; June 4; 163x 41
34 Same sample as Figure 33; 407x 41
35 Site M-14; Impactor Stage 4; June 4; 163x 42
36 Same sample as Figure 35, rotated 90° to show structure of
recrystallized mass; 163x 42
37 Same sample as Figure 35; 407x 43
38 Site M-14; Impactor Stage 5; June 4; 163x 43
39 Same sample as Figure 38; 407x 44
40 Site M-14; Impactor Stage 6; June 4; 163x 44
41 Same sample as Figure 40; 407x 45
42 Site M-14; Impactor Stage 7; June 4; 163x 45
43 Site M-10; Hi-vol; June 11; 163x, 46
44 Site M-10; Impactor Stage 0; June 11; lOOOx 46
45 Site M-10; Impactor Stage 4; June 11; lOOx 47
46 Enlargement of Figure 45; lOOOx 47
47 Enlargement of Figure 46; 10,000x 48
48 X-ray spectrum of total Stage 4 deposit site (Figure 45) 48
49 Site M-10; Impactor Stage 7; June 11; lOOx 49
50 Enlargement of ammonium sulfate ring crystals from Figure 49;
lOOOx 49
51 Enlargement of particles in center of deposit in Figure 49;
lOOOx 50
52 Enlargement of crusted deposit from Figure 49; 10,000x 50
53 X-ray spectrum of center of deposit (shown in Figures 49
and 52) 51
54 Site M-ll; Hi-vol; June 11; 163x 51
vn
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FIGURES (continued)
Number Page
55 Same sample as Figure 54 with polars completely crossed to
show birefringent spherical particles; 407x 52
56 Site M-ll; Impactor Stage 3; June 11; 300x 52
57 X-ray spectrum of whole deposit pictured in Figure 56 53
58 Enlargement of Figure 56; 3000x 53
59 Site M-ll; Impactor Stage 7; June 11; 300x 54
60 Site M-14; Hi-vol; June 11; 163x 54
61 Same sample as Figure 60; 407x . . 55
62 Site M-14; Impactor Stage 0; June 11; 3000x 55
63 Site M-14; Impactor Stage 3; June 11; X-ray spectrum of whole
sample 56
64 Site M-14; Impactor Stage 3; June 11; 3000x 56
65 Site M-14; Impactor Stage 7; June 11; 300x 57
Vlll
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TABLES
Number Page
1 Impactor Cut Size, D 18
2 Samples Received for Analysis 19
3 Composition of Hi-vol Samples 21
4 Elemental Concentrations, yg/m3 22
5 Compound Concentrations, yg/m3 23
6 Percentage of TSP by Compound 24
IX
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ACKNOWLEDGMENTS
The aerosol samples taken in Miami, Florida, during June of 1975 were
collected jointly by the U.S. Environmental Protection Agency and Dr. Kenneth
Hardy of Florida International University.
Elemental concentration data, determined by Drs. Jack Winchester and
William Nelson of Florida University, are used in this report and gratefully
acknowledged.
x
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SECTION 1
RECOMMENDATIONS
Following a review of the microscopical analyses, it was noted that an
alternate method of analysis would have been feasible. The major compounds
in the samples could have been identified quantitatively by means of microscop-
ical petrography. Ammonium sulfate, calcite, quartz, carbonaceous particles,
and the feldspars could have been analyzed sequentially as follows.
1. Determine the total projected area of all birefringent particles
(measurement A). These would include ammonium sulfate, calcite,
quartz, and feldspars.
2. Dissolve the ammonium sulfate in water and determine the projected
area for the remaining birefringent particles (measurement B). The
difference between measurement A and measurement B is the projected
area of ammonium sulfate.
3. Dissolve the calcite in dilute acid and determine the remaining pro-
jected area (measurement C). The difference between measurement B
and measurement C is the projected area of calcite. The remaining
projected area of birefringent particles is due to quartz and the
feldspars. (This method may also be used to determine the particle
size distribution of the components.)
4. Determine the projected area for the opaque carbon compounds such
as vehicle exhaust, rubber tire fragments, and oil soot. The rubber
tire fragments and oil soot can be distinguished from vehicle exhaust
carbon by particle size discrimination. The spherical oil soot and
cigar-shaped rubber tire fragments can be distinguished by their shape
factors.
1
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This method of analysis could account for more than 80 percent of the
total aerosol mass. Each step requires approximately 10 minutes plus elapsed
time for dissolution or chemical reaction. These analyses could be performed
on glass fiber filters but ideally should be done on transparent, isotropic
membrane filters. The Nuclepore Corporation of Pleasanton, California, has
developed pilot batches of a transparent, isotropic, polycarbonate filter which
could be ideal for this task.
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SECTION 2
SAMPLING PROCEDURES
Aerosol samples were collected in Miami, Florida, between June 4, and 12,
1975. Three sampling sites were selected and designated M-10, M-ll, and M-14.
Site M-10, 6400 N.W. 27th Ave., was a U.S. Marine Corps Station. Site M-ll,
251 E 47th St., was located at Hialeah High School. Site M-14 was a fire sta-
tion at 6000 S.W. 87th Ave.
Hi-vol samplers and eight-stage Andersen impactor samplers were used to
collect aerosol samples at the three sites. The aerosol cut-off size, D ,
for each impactor stage is shown in Table 1. Samples for microscopical analysis
were collected on June 4, 11, and 12. The original sampling protocol called
for the use of Millipore membrane filters on Stages 0-4 and Nuclepore membrane
filters on Stages 5-7 of the impactor samples. Millipore filters were to be
used as backups. Inadvertently, Millipore filters were used for all eight stages
during the first day of sampling (June 4), and Nuclepore poreless filters were
used for all eight stages during the remaining two days of sampling (June 11
and 12).
Nuclepore filters are birefringent and thus interfer with polarized light
microscopical studies of particles. Therefore, detailed optical microscopic
studies could be made on the June 4 samples only. Table 2 lists the samples
submitted for microscopical analysis.
SAMPLE PREPARATION FOR OPTICAL AND SCANNING ELECTRON MICROSCOPY
Hi-vol Sample Preparation
Wedge-shaped sections were cut from each filter and placed on glass slides.
They were then immersed in a liquid with a refractive index of 1.515. The liquid
3
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matched the refractive index of the glass fibers, rendering them invisible dur-
ing the ensuing examination by optical microscopy.
Andersen Impactor Sample Preparation
Sections of 10 mm by 35 mm were cut from the Millipore filter substrates
and immersed in 1.515 refractive index liquid on glass slides. Deposits on
the Nuclepore filters were examined dry on the uncut filters by both transmitted
and reflected light.
Scanning Electron Microscopy
Small sections of selected filters from the impactor samples were mounted
on carbon stubs for scanning electron microscopy (SEM) and x-ray fluoresence
analysis. Samples collected on both Millipore and Nuclepore membrane filter
substrates were analyzed by these two methods. The hi-vol filter samples
were analyzed by optical microscopy only.
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SECTION 3
MICROSCOPICAL SAMPLE ANALYSIS
ANALYSIS OF SAMPLES COLLECTED JUNE 4, 1975
The glass fiber hi-vol filters were used to semi-quantitatively estimate
the concentrations of specific aerosols. The estimates, based on percentages
of total mass, are shown in Table 3. Although glass fiber filters are not
ideal for optical polarized light microscopy, it is important to use a total
sample to correctly determine the ratio of aerosol types present.
The Andersen impactor samples were submitted to both SEM and optical
microscopy. The impactor samplers were especially important to this study,
since they provided the key to the impact from ocean spray. From the many
aerosol samples examined by the authors, the impactor samples were the only
ones to show that calcium carbonate can form from water droplets containing
calcium ions. This observation would not have been possible without the avail-
ability of the impactor samples.
Site M-10 Samples
Hi-vol Sample
The sample consisted primarily of calcium carbonate particles in both a
natural and recrystallized form (Figure 1). A few large, freshly cleaved
quartz particles were present. Numerous large rubber tire particles and a
great number of fine carbonaceous particles from automobile emissions were also
contained in the sample. Oil soot and carbonized flakes from an incinerator
type combustion source were trace sample components. Large sheets of decaying
vegetation were a minor sample component. Definite sea salt crystals
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Automobile traffic was the primary source for suspended mineral particles,
as is evidenced by the large number and sizes of rubber tire particles. Ocean
salt spray was also probably a major source of the TSP. However, it was ex-
tremely difficult to ascertain exactly what proportion of the collected parti-
cles was due to the ocean salt spray, because the calcium carbonate particles
were generated by both automobile traffic and salt spray.
Andersen Impactor Sample
Stages 0, 1, 2, and 3 each contained more mass than the comparable stages
at Sites M-ll and M-14. The presence of many particles larger than the impac-
tor stage cut size (Figure 2) indicates that a higher percentage of the sample
consisted of recrystallized calcium carbonate. To prove that the recrystallized
material present on Stage 4 was calcium carbonate, a filter segment was treated
with dilute hydrochloric acid. Bubbles formed in the sample, indicating the
evolution of CO . After drying, most of the birefringent material (calcium
carbonate) was absent (Figures 3 and 4). Stages 5 through 7 were similar in
composition to the M-ll and M-14 impactor samples. However, the higher mass
loadings on the M-10 sample permitted the growth of several very large ammonium
sulfate crystals on Stage 7 (Figure 5).
Scanning Electron Microscopy
Stage 0An x-ray area scan of the entire particle deposit
revealed calcium as the only peak distinguishable over
background noise. X-ray analyses of individual particles
confirmed the presence of rubber tire dust, quartz, feldspar,
and iron oxide particles. Morphology indicated that many
of the calcium containing particles were recrystallized
on the filter surface from liquid (Figure 6). X-ray analyses
of these particles confirmed they were calcium carbonate, since
calcium was the only element present in the x-ray analyses.
Stage 3Calcium again was the primary element detected on an
area x-ray scan of the particle deposit. However, distinct
peaks for sulfur and chlorine (30 to 50 percent lower than
calcium) were also noted above the background. X-ray analyses
of discrete particles revealed the presence of calcium carbon-
ate, calcium sulfate, calcium chloride, mixed calcium chloride-
sulfate, potassium calcium phosphate, magnesium chloride, quartz,
and feldspar particle types (Figures 7 and 8).
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Stage 5An area scan of the deposition site revealed the
presence of magnesium, aluminum, silicon, sulfur, potassium,
calcium, and iron (Figures 9 and 10). Many large, cubical
particles were found. Compositions varied from calcium
carbonate to calcium chloride-sulfate, depending on the
amount of matrix material surrounding the cubes (Figures
11-14). Particles toward the center of the impactor spot
tended to be the calcium chlorides and carbonates. More
sulfate species were present on the edges of the deposition.
None of the very large recrystallized masses seen by optical
microscopy were present in the deposits examined by SEM.
Stage 7The very large, flat, rectangular crystals seen by
optical microscopy were present in the deposits examined by
SEM. They were primarily ammonium sulfate with a trace of
potassium (Figures 15-17).
Back-upSulfur was the only peak distinguishable over the
background in an area x-ray scan of the sample. Discrete
particles containing various combinations of lead, bromine,
chlorine, iron, and calcium were also detected by fixed
spot analysis.
Site M-ll Samples
Hi-vol Sample
Although calcium carbonate again was the primary particle type present, the
concentrations of quartz, rubber tire dust, and fine carbonaceous particles ap-
pearing on the M-ll sample (Figure 18) were higher than those present on the
M-10 sample. Recrystallized ammonium sulfate particles were also present in
slightly higher concentrations compared to the M-10 samples. Other particle
types exhibited comparable concentrations. Overall particle size was smaller
on the M-ll sample, which probably accounted for the lower mass loading.
Automobile traffic was the primary generator of particles found on the
sample. The auto influence was much stronger on this sample than on the M-10
sample. Ocean spray salt was present, but its contribution to total sample
mass was difficult to assess.
Andersen Impactor Sample
Stage 0 contained more large rubber tire particles and less recrystallized
calcium carbonate (Figure 19) than did Stage 0 at Site M-14. This observation
7
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was expected, since Site M-ll showed the highest automobile traffic influence
on the hi-vol samples.
Stages 1 and 2 contained progressively more material, with higher percent-
ages of calcium carbonate and lower percentages of rubber tire dust. Stage 3
was similar to Stage 3 at M-14 in that large prisms and dendrites of calcium
carbonate had begun to appear (Figure 20). As on the M-14 sample, Stages 4
and 5 contained extremely large masses of recrystallized calcium carbonate
(Figures 21 and 22). Ammonium sulfate crystals began to appear on Stage 5.
Stage 6 contained significantly more sulfate (Figure 23) than did the
M-14 sample at Stage 6. Tailpipe emissions were the other major particle type
present. Each deposition site (on Stage 7) contained very large crystals of
ammonium sulfate along with many carbonaceous particles (Figures 24 and 25).
Site M-14 Samples
Hi-vol Sample
This sample was closer in composition to the M-10 sample than to the M-ll
sample. Calcium carbonate was the primary particle type present (Figures 26
and 27). Automobile related particles were also a major component. Recrystal-
lized ammonium sulfate particles were present in slightly higher concentrations
on this sample than on the M-10 sample.
As with the samples from the other two sites, automobile traffic was the
major source for the collected particles. Again, however, ocean spray salt
may have been a significant contributor to the TSP levels.
Andersen Impactor Sample
Stage 0 was composed primarily of calcium carbonate, both natural and
recrystallized. Rubber tire dust was present in large amounts (Figure 28).
A minor amount of quartz was also present. Approximately 30 percent of the
calcium carbonate present was recrystallized from liquid droplets (Figure 29).
Modal size for particles on this stage was 10 pm.
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Stage 1 was similar in composition to Stage 0. However, a higher percent-
age of the calcium carbonate was recrystallized compared to the Stage 0 sample.
Modal particle size was approximately 8 ym (Figure 30).
Stage 2 contained significantly more particles than the first two samples.
Calcium carbonate remained the primary sample component, and significant amounts
of rubber tire dust were also still present (Figure 31). Oil soot was also
present on this stage. The concentrations of glassy fly ash and biological
particles were higher than those on the previous two stages. Modal particle
size was approximately 5 ym (Figure 32).
More material appeared on Stage 3 than on Stage 2. Calcium carbonate was
present in higher concentrations than on the previous stages, and very large
recrystallized calcium carbonate particles had begun to appear (Figure 33).
That these particles were recrystallized is evidenced by their very large size
compared to the rest of the particles (Figure 34). Rubber tire dust decreased
in concentration, and clumps of fine carbonaceous tailpipe particles appeared.
Stage 4 contained huge crystals of regrown calcium carbonate. The recrys-
tallized material comprised at least 6 percent of the mass on the stage (Figures
35 and 36). The concentration of carbonaceous particles primarily derived from
tailpipe emissions increased. Modal particle size, as indicated by the fly
ash spheres, was approximately 2 ym (Figure 37).
One large recrystallized calcium carbonate mass composed most of Stage 5
(Figure 38). Carbonaceous auto exhaust particles were the second most abundant
particle type present (Figure 39). A second type of recrystallized particle
began to appear on this stage, and small ammonium sulfate crystals were present.
Carbonaceous (tailpipe) particles were the major components of Stage 6
(Figure 40) . Small amounts of recrystallized ammonium sulfate particles were
also present (Figure 41) .
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Stage 7 was composed primarily of large thin sheets of recrystallized
ammonium sulfate (Figure 42). Tailpipe emissions were the second most abundant
particle type by mass.
The back-up filters contained carbonaceous particles and a few fine
mineral particles only.
ANALYSIS OF SAMPLES COLLECTED JUNE 11, 1975
Site M-10 Samples
Hi-vol Sample
The sample was composed primarily of calcium carbonate. In comparison to
the June 4 sample a higher percentage of the carbonate in this sample was re-
crystallized from liquid droplets (Figure 43). Although automobile related
particles were lower in concentration compared to the June 4 sample, automobile
traffic was still the primary source for particles found in the sample. The
major difference between the June 4 and June 11 samples was the presence of
great numbers of small (1 ym-3 ym), highly birefringent, spherical particles on
the June 11 samples. These spheres were recrystallized particles of ammonium
sulfate, calcium carbonate, and calcium sulfate. Their presence indicated a
significant ocean spray salt contribution to the TSP level on this date.
Andersen Impactor Sample
Each stage of the M-10 sample contained more mass than comparable stages
at Sites M-ll and M-14. M-ll and M-14 samples were relatively similar in com-
position; M-10 samples differed slightly from these.
Stages 0-3 were composed primarily of recrystallized salt particles. Stage
1 showed a lower percentage of recrystallized material compared to the same stage
of the M-ll and M-14 samples. Stage 4 contained very large recrystallized cal-
cium carbonate masses. Stages 5 and 6 were so heavily loaded with material that
it was impossible to determine particle morphologies. The Stage 7 deposits
consisted of several huge ammonium sulfate crystals forming a ring around a
carbonaceous particle center.
10
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Scanning Electron Microscopy
Stage 0Many well-formed, recrystallized particles were found
on this stage (Figure 44). Calcium was the primary element pres-
ent. It occurred in carbonate, sulfate, and chloride forms; it
also appeared in mixed particles with chlorine and potassium, or
chlorine and sulfur. Discrete particles of sodium chloride and
magnesium chloride were also present.
Stage 4--Particles on this stage were frequently discrete parti-
cles deposited as solids (Figures 45-47) rather than liquids,
compared to this stage on June 4. X-ray scans of the entire
deposition site indicated silicon was the major sample component
(Figure 48). The composition of the deposit varied considerably
from the center to the edges.
Stage 7A deposition site composed of a dark, carbonaceous
center mass surrounded by large crystals (10 to 30 ym ammonium
sulfate) was analyzed by SEM (Figure 49). The large crystals
showed only suflur when x-rayed (Figure 50). Large, snowball-
like clusters in the center of the deposition were primarily
ammonium sulfate; trace quantities of sodium were detected in
these particles (Figure 51). The center of the deposition area
contained primarily sulfur, with silicon, aluminum, potassium,
calcium, and iron (listed in order of decreasing abundance)
also present (Figures 52 and 53).
Site M-ll Samples
Hi-vol Sample
As on June 4, automobile related particles were higher in concentration
on the M-ll sample than on the M-10 and M-14 samples (Figure 54). The sample
was quite similar in composition to the June 4, M-ll sample. Calcium carbonate
was the primary particle type present. The fine, spherical, highly birefringent
particles seen on the June 11, M-10 sample were also present in large numbers
on the M-ll sample (Figure 55). Ocean salt spray contributed approximately
30 percent of the sample mass.
Andersen Impactor Sample
Stages 0 through 3 each contained more total mass than did the comparable
M-14 samples for this date. Recrystallized rhombs and dendrites of calcium
carbonate, sodium chloride, potassium chloride, and calcium chloride contained
the majority of the sample mass on these stages. Rubber tire dust was also a
11
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major component on Stages 0-3. Stage 4 contained a very large recrystallized
calcium carbonate mass similar to the one seen on Stages 4 and 5 of the M-14
sample. Particles on Stages 5 and 6 were piled heavily on top of each other,
precluding the determination of particle morphology. Stage 7 contained huge
ammonium sulfate crystals in the center of the main deposition site. Carbona-
ceous particles were major components of Stages 4 through 7.
Scanning Electron Microscopy
Stage 0Calcium was the primary element present. A lower
percentage of the recrystallized calcite particles was pre-
sent compared to the M-10 sample. A larger amount of mag-
nesium, sodium, and potassium, chlorides and sulfates was
present on this stage at Site M-ll than on Stage 0 for the
June 11, M-10 sample.
Stage 3Silicon, aluminum, chlorine, sulfur, and calcium
were the primary elements found in the recrystallized particle
mass (Figures 56 and 57). Many well formed sodium chloride
cubes were present (Figure 58).
Stage 7Sulfur was the primary element detected in an x-ray
scan of the total deposition; very small amounts of silicon,
aluminum, potassium, calcium, sodium, iron, lead, and bromine
were also detectable over the background. The major recrystal-
lized species present was ammonium sulfate (Figure 59).
Site M-14 Samples
Hi-vol Sample
Ocean salt spray was present in the heaviest concentration on this sample,
representing 30 to 40 percent of the sample mass (Figure 60). Automobile re-
lated particles, including rubber tire dust, tailpipe emissions, and roadway
pavement, were major sample components. Calcium carbonate was the primary
particle type. As on the other two samples for this date, large numbers of
small, highly birefringent, spherical calcite particles were present (Figure
61).
Andersen Impactor Sample
All stages were composed primarily of recrystallized particles. On Stages
0 through 3, the recrystallized particles were discrete rhombs and dendrites of
12
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calcium carbonate, sodium chloride, potassium chloride, and calcium chloride.
As did the Millipore filter samples, the Nuclepore samples on Stages 4 and 5
contained massive crystals of calcium carbonates. The samples on Stages 6 and
7 were very similar to the M-14 samples for June 4. A few very small sulfate
crystals were present on Stage 6, whereas Stage 7 contained thin, flat sheets
of recrystallized ammonium sulfate. Carbonaceous particles were the primary
sample components on Stages 6 and 7 and major sample components on Stages
4 and 5.
Scanning Electron Microscopy
Stage 0Recrystallized calcium carbonate, sodium chloride,
and calcium chloride were the major particle types found on
this stage (Figure 62).
Stage 3This sample was very similar in composition to the
Stage 3, M-ll sample of June 11 (Figure 63). However, more
of the particles were either recrystallized or cemented to-
gether by a sheet of recrystallized material (Figure 64).
Stage 7As with other Stage 7 samples, sulfur was the only
element detectable over the background. The particle deposit
was a thin sheet of ammonium sulfate, which encapsulated fine
carbonaceous and mineral particles (Figure 65). Lead was
undoubtedly present in the fine carbonaceous auto exhaust
particles but was not detected with an area x-ray emission
scan.
ANALYSIS OF SAMPLES COLLECTED JUNE 12, 1975
Brief examinations of the various time period samples from June 12 indi-
cated only minor differences between these samples and those collected on the
other dates. The M-10 sample showed the heaviest particle loading on all stages.
Recrystallized salt particle concentration increased from Stage 0 to Stage 5.
Because of shorter sampling time periods and therefore fewer particles, the
massive calcium carbonate sheets were present on the Stage 5 samples only. As
on the other sampling days, the Stage 7 samples from all three sites primarily
contained large recrystallized ammonium sulfate sheets and particles, and fine
carbonaceous (tailpipe) particles.
13
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SECTION 4
COMPARISON OF MICROSCOPICAL AND ELEMENTAL DATA
Aerosol samples for proton induced x-ray emission analysis were collected
simultaneously with the hi-vol and impactor samples at each of the three sites.
These samples were collected in 2-hour sequential periods from midnight to mid-
night of each sampling day.
The elemental data from each of these 2-hour samples were averaged for
the 24-hour sampling period to compare these results (Table 4) to the microscopy
results. Each element was converted to its most probable compound or combining
form (Table 5). These conversions are not exact since major elements such as
calcium, sulfur, and silicon occur in several different compounds. However,
the conversions are probably very close to the correct mass concentration for
the samples, because the elements were converted to their most abundant compound
or combining form in the samples. As a final step, to permit comparisons, the
percentage of each compound in the sample was calculated (Table 6).
X-ray emission analysis showed that the total percentage of elements in
compound form ranged from 7.4 to 47.7 percent. This calculation left an un-
accounted balance ranging from 92.6 to 52.3 percent. Approximately 30 to 40
percent of this unaccounted balance was traceable to organics such as rubber
tire fragments, carbonaceous auto and truck exhausts, and biological plant
tissue. However, organics did not account for all the missing percentages.
In fact, as the TSP mass concentration increased, the elemental concentration
decreased. This inconsistency may have been caused by a large particle sampling
bias, because the samples with higher mass concentrations were composed pri-
marily of particles larger than 10 ym. Even if these large particles had been
sampled proportionately, they probably would have yielded lower elemental
concentrations resulting from x-ray self absorption effects. A decrease in
14
-------
elemental concentrations also could have occurred for smaller particles, which
tend to dissolve and recrystallize into large particles (such as was seen in
each of the samples analyzed microscopically).
In spite of these differences, the elemental data showed a semi-quanti-
tative trend in agreement with the microscopy results. Calcium (as calcite
and feldspars) was the major component in each of the samples. Silicon and
aluminum were also major elements. Silicon occurred in quartz and with aluminum
as clays and feldspars. Sulfur was present principally as ammonium sulfate,
then as calcium sulfate (gypsum). It also appeared in the rubber tire frag-
ments .
Chlorine was present mainly as halite but also was found with calcium and
magnesium as simple salts. The remaining elements were trace components of the
samples, perhaps with the exception of phosphorous. Phosphorous was not de-
tected in any of the mineral particles and was attributed to biological plant
material, where it is usually found. Vanadium was detected exclusively in the
oil soot particles. Titanium was found in some of the recrystallized salt parti-
cles but usually was present in glassy fly ash spheres from coal combustion and,
of course in clay minerals. The titanium in these samples undoubtedly derived
from clays encapsulated during crystallization of some of the salt particles.
We did not calculate the mass contribution from iron, manganese, nickel,
chromium, strontium, and bromine, since it accounted for less than 2 yg/m3 in
each 24-hour sample.
15
-------
SECTION 5
RESULTS
The results of this study show automobile traffic and ocean spray were the
primary sources of atmospheric aerosol in the Miami metropolitan area. Surpris-
ingly, resuspended mineral particles from roadway surfaces rather than direct
emission particles (i.e., rubber tire dust and tailpipe emissions) were the
major contributants of automobile traffic. Recrystallized particles of sodium,
magnesium, potassium, calcium, titanium, and carbonates, chlorides and sulfates
were contributed by the ocean spray. These particle types were present in the
air both as liquids and as dried solids. Since the ammonium sulfate forms
appeared primarily on the smaller particle stages of the Andersen impactor
samples, this compound more likely emanated from fossil fuel of automobiles
and power plants than from ocean spray.
Sample compositions were very similar at the three sites; however, the
degree of impact from the two sources varied. Site M-ll showed the greatest
influence from automobile traffic, as was indicated by the large sizes and
amounts of rubber tire dust present. Sites M-ll and M-14 exhibited a greater
effect from ocean spray than did Site M-10.
The effect of the ocean spray was greater on the June 11 samples with the
resultant wind direction from 100° than on the June 4 samples, when the resul-
tant wind was from 340°. In fact, the increased TSP loadings on the June 11
samples appeared to be caused primarily by ocean spray.
The Andersen impactor samples provided invaluable information about the
sources of the Miami atmospheric aerosol. Although the hi-vol samples con-
tained large numbers of calcium carbonate particles, it was recognizable only
on the impactor samples that at least 20 percent of the calcium carbonate
16
-------
particles present were crystallized from liquid droplets. Since calcium car-
bonate is essentially insoluble in water, the calcite must have formed on the
impactor stages. This hypothesis is corroborated by the observation that these
crystallized calcite particles have a particle size which is 10 times greater
than the D cut size of the impactor stage on which they formed.
The logical source of the droplets providing calcium ions is ocean spray.
However, the samples did not contain the same ratio of sodium and magnesium to
calcium as found in ocean water (26 and 3 respectively). This discrepancy
suggests that some of the spray droplets may have been from fresh water sources.
Approximately 70 percent by mass of the atmospheric aerosol in Miami is
below 3 ym in size.
17
-------
TABLE 1. IMPACTOR CUT SIZE, D
Stage
0
1
2
3
4
5
6
7
8
D50'
16
9
5.
2.
1.
0.
0.
0.
back-up
*
ym
.4
.3
35
95
53
95
54
38
filter
*
D_n values for Stages 2 through 6 determined by Flesch, et al., other D
values are calculated.
The backup filter was a 0.8 ym pore size, cellulose triacetate membrane
(Millipore) filter.
18
-------
TABLE 2. SAMPLES RECEIVED FOR ANALYSIS
Date
6/4/75
6/4/75
6/4/75
6/4/75
6/4/75
6/4/75
6/4/75
6/4/75
6/4/75
6/4/75
6/4/75
6/11/75
8/11/75
6/11/75
6/11/75
6/11/75
6/11/75
6/11-12/75
6/11-12/75
6/11-12/75
6/11/75
6/12/75
6/12/75
6/12/75
6/12/75
6/12/75
Sampling
Period,
Hours
0000-2351
0000-2351
0000-2351
0000-2341
0002-2346
0002-2346
0001-2359
0047-2350
0047-2350
0047-2350
0010-2345
0004-2400
0004-2400
0000-2330
0014-2347
0014-2347
0003-2400
0125-0145
0125-0145
0125-0145
0102-2537
0000-0600
0000-0600
1345-15455
1345-1545
0000-2348
Site
M-10
M-10
M-10
M-10
M-ll
M-ll
M-ll
M-14
M-14
M-14
M-14
M-10
M-10
M-10
M-ll
M-ll
M-ll
M-14
M-14
M-14
M-14
M-10
M-10
M-10
M-10
M-ll
Sampler
Type
Impactor
Impactor
Impactor
Hi-vol
Impactor
Impactor
Hi-vol
Impactor
Impactor
Impactor
Hi-vol
Impactor
Impactor
Hi-vol
Impactor
Impactor
Hi-vol
Impactor
Impactor
Impactor
Hi-vol
Impactor
Impactor
Impactor
Impactor
Impactor
Stages
0-7
Backup
Backup
TSP
0-7
Backup
TSP
0-7
Backup
Backup
TSP
0-7
Backup
TSP
0-7
Backup
TSP
0-7
Backup
Backup
TSP
0-7
Backup
0-7
Backup
0-7
Sample
Numbers
011-018
019
020
. 00563
020-027
028
00564
021-028
029
030
00562
071-078
079
00621
074-081
082
00620
091-098
099
100
00619
PO-P7
P8
P1-P8
P9
083-090
Substrate
Type
Millipore
Millipore-1
Millipore-2
Glass Fiber
Millipore
Millipore 1
Glass Fiber
Millipore
Millipore-1
Millipore-2
Glass Fiber
Nuclepore
Millipore-1
Glass Fiber
Nuclepore
Millipore-1
Glass Fiber
Nuclepore
Millipore-1
Nuclepore- 2
Glass Fiber
Nuclepore
Millipore-1
Nuclepore
Millipore-1
Nuclepore
19
-------
TABLE 2. SAMPLES RECEIVED FOR ANALYSIS (continued)
Date
6/12/75
6/12/75
6/12/75
6/12/75
6/12/75
6/12/75
6/12/75
Sampling
Period,
Hours
0000-2348
0230-0600
0230-0600
1300-1530§
1300-1530
1605-2000
1605-2000
Site
M-ll
M-14
M-14
M-14
M-14
M-14
M-14
Sampler
Type
Impactor
Impactor
Impactor
Impactor
Impactor
Impactor
Impactor
Stages
Backup
0-7
Backup
0-7
Backup
0-7
Backup
Sample
Numbers
091
101-108
109
111-118
119
120-127
128
Substrate
Type
Millipore-1
Nuclepore
Millipore-1
Nuclepore
Millipore-1
Nuclepore
Millipore-1
1 = 47 mm diameter
2 = 37 mm diameter
*
§
Inversion
PO-P1, P8, P1-P8, and P9 were
static Precipitator.
special runs involving TSI model 3100 Electro-
20
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24
-------
Figure 1. Site M-10; Hi-vol; June 4; (Note large rubber tire fragments);
Slightly uncrossed polars (SUP); 163x.
r
Figure 2. Site M-10; Impactor Stage 3; June 4; SUP; 163x.
25
-------
Figure 3. Site M-10; Impactor Stage 4; June 4; SUP; 163x.
' *w
>' v,r
U.
T*~ it » -'* *>
a. - 4-i*- '/"f'|fc;^*%lif.^
mi .-;4- 'i\«v:;>v»^-:'.:
Fv" -" -# ^4^t*^'
sfrc.v-"*4, !*,*** % »7 <*'^VTL.K;
I'" -1- *
> -^nx ':^^:*m':
v %
* .%
fc * f
%
*
%
It
Figure 4. Same sample as Figure 3 after HC1 wash. SUP; 163x.
26
-------
Figure 5. Site M-10; Impactor Stage 7; June 4; SUP; 163x.
Figure 6. Site M-10; Impactor Stage 0; June 4; (recrystallized calcium car-
bonate) ; Secondary electron image (SEI); SOOOx.
27
-------
Figure 7. Site M-10; Impactor Stage 3; June 4; SEI; lOOOx.
. IK KBWBK-MV
iHiiiiiimiiiiiiiiiiiiimiiiiiiimiiimiiiiiii,
IIIIIHIIIIIIIIIII iiimmmiiiimiffliiiiiiiii
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Figure 8. X-ray spectrum of large center particle in Figure 7.
28
-------
Figure 9. Site M-10; Impactor Stage 5; June 4; SEI; lOOOx.
Figure 10. X-ray spectrum of deposition site on Stage 5, Figure 9; Peaks are
Mg, Al, Si, S, Cl, K, Ca, and Fe.
29
-------
r
4'
,1
'<
Figure 11. Enlargement of upper cubes in Figure 10; SEI; 3000x.
Figure 12. X-ray spectrum of cubes in Figure 11; Three peaks from left to
right are S, Ca, and Fe.
30
-------
Figure 13. Enlargement of lower left cubes in Figure 9; SEI, 3000x.
CM MM S*Stt INT
FS- * KIWIX-RftV US* tMV/CN
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62 84 86 88 It 12 14 16 18
Figure 14. X-ray spectrum of cubes in Figure 13.
31
-------
- % -'I"
," 3$ ,a i%
Figure 15. Site M-10; Impactor Stage 7; June 4; (Large ammonium sulfate
crystals); SEI; 300x.
Figure 16. Enlargement of one crystal shown in Figure 15; SEI; SOOOx.
32
-------
Irs- »_
1CM4 INT
KIVIX-MY Mf tMV'CN
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-------
*
*
* , **'
Figure 19. Site M-ll; Impactor Stage 0; June 4; (Compare to Figure 28 and
note larger amounts of rubber tire dust in Figure 19); SUP; 163x.
* ''
,* » "
* * «
-*.
'<(<*-'
'' '
-)>_ 0 ^Ik fl__
t 7^
*%*'
Figure 20. Site M-ll; Impactor Stage 3; June 4; SUP; 407x.
34
-------
Figure 21. site M-ll; Impactor Stage 4; June 4; (Massive white particles are
recrystallized calcium carbonate); SUP; 163x.
Figure 22. Site M-ll; Impactor Stage 5; June 4; SUP; 407x.
35
-------
p *-2T «
i
-------
Figure 25. Same sample as Figure 24 with polars crossed to show large
ammonium sulfate crystal; 163x.
Figure 26. Site M-14; Hi-vol; June 4; SUP; 163x.
37
-------
-o-/ *;-
» ;5 r-'-Ti-j 'Si**" i-TMlV- V
***. v-'j»** -s
ps *«spssiji
k" ^.,;,... * t-, .-<«».-.*;
j-t- ^ .j =*:, ' » ' '!"""*- .fo* ;':»i--J,,iVJ|'*1li'
^;>>^k*i- ,-' *
<"..-wBfc '"^' i»
Figure 27. Same sample as Figure 26; SUP; 407x.
Figure 28. Site M-14; Impactor Stage 0; June 4; SUP; 163x.
38
-------
r
Figure 29. Same sample as Figure 28 showing group of particles recrystal-
lized from liquid; SUP; 407x.
r
*
/
Figure 30. Site M-14; Impactor Stage 1; June 4; SUP; 163x.
39
-------
r
Figure 31. Site M-14; Impactor Stage 2; June 4; SUP; 163x.
W
«..- '.<»<*
' ??*'- * '
*»,
n
J
Figure 32. Same sample as Figure 31; SUP: 407x.
40
-------
r
Figure 33. Site M-14; Impactor Stage 3; June 4; (Note large birefringent
white particles, which are recrystallized calcium carbonate);
SUP; 163x.
* *-' 'f< %fe'* * '**"'- "**"
, > ' * *-": v"-
- ; - A .^ 4,*
<:.' >---.aO
"v*^,-* *-'l * * '? < ~.. . i%',,^.
* ^ ', * ,* &' -. .u A » " ' *^****^% **
TW^- <*f. ''-,"f.-; v».*t-,~.Jf.
* '*. "*^! ~ ;"/
Figure 34. Same sample as Figure 33; SUP; 407x.
41
-------
r
* ",
M
Figure 35. Site M-14; Impactor Stage 4; June 4; (Note large masses of re-
crystallized calcium carbonate); SUP; 163x.
r
Figure 36. Same sample as Figure 35, rotated 90 to show the structure of
recrystallized mass; SUP; 163x.
42
-------
Figure 37. Same sample as Figure 35; SUP; 407x.
Figure 38. Site M-14; Impactor Stage 5; June 4; (Large white mass is re-
crystallized calcium carbonate; small white particles are re-
crystallized sulfate); SUP; 163x.
43
-------
72
Figure 39. Same sample as Figure 38; SUP; 407x.
r
» t ',
Figure 40. Site M-14; Impactor Stage 6; June 4; SUP; 163x.
44
-------
Figure 41. Same sample as Figure 40, showing fine recrystallized sulfate
particles; SUP; 407x.
Figure 42. Site M-14; Impactor Stage 7; June 4; (White material is recrystal-
lized ammonium sulfate); SUP; 163x.
45
-------
%
,
*. r»* s *
?'%*>
*
Figure 43. Site M-10; Hi-vol; June 11; SUP; 163x.
Figure 44. Site M-10; Impactor Stage 0; June 11; Nuclepore substrate; SEI;
lOOOx.
46
-------
Figure 45. Site M-10; Impactor Stage 4; June 11; Nuclepore substrate; SEI;
lOOOx.
Figure 46. Enlargement of Figure 45; SEI; lOOOx.
47
-------
Figure 47. Enlargement of Figure 46; SEI, 10,000x.
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mum mmiii
iiiiiiii 11 mm
limn 11 mm iiiiiimiiiiiiiiiiiiiiiiiiiiiii
mini ii mm iiiiiiiiiiiiiiiiiiiiiiiiiiniiii
mm* ('ii'1 ^iiiiiiiiiiFiiiiiiiiiiiiiiiiii
iiiiir ' umii iiiiiuiiiiiiillli
Figure 48. X-ray spectrum of total Stage 4 deposit site (Figure 45); Peaks
visible are Mg, Al, Si, S, Cl, K, Ca, Ti, and Fe.
48
-------
Figure 50. Enlargement of ammonium sulfate ring crystals from Figure 49;
SEI; lOOOx.
Figure 49. Site M-10; Impactor Stage 7; June 11; Ammonium sulfate crystals
surrounding main deposition area; Nuclepore substrate; SEI; lOOx.
49
-------
Figure 51. Enlargement of particles in center of deposit in Figure 49- SEI-
10,000x.
Figure 52. Enlargement of crusted deposit from Figure 49; SEI; 10,000x.
50
-------
Figure 53. X-ray spectrum of center of deposit (shown in Figures 49 and 52);
Peaks for Al, Si, S, K, Ca, and Fe are present.
*» m
.Figure 54. Site M-ll; Hi-vol; June 11; SUP; 163x.
51
-------
Figure 55. Same sample as Figure 54 with polars completely crossed to show
birefringent spherical particles; 407x.
Figure 56. Site M-ll; Impactor Stage 3; June 11; Nuclepore substrate; SEI;
300x.
52
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mi mi minimi
Figure 57. X-ray spectrum of whole deposit pictured in Figure 56; Elemental
peaks are for Na, Mg, Al, Si, S, Cl, K, Ca, Ti, and Fe.
Figure 58. Enlargement of Figure 56; (Large crystal is primarily NaCl with
traces of S, Mg, Cl, and Ca, and therefore is sea salt); SEI; 3000
SOOOx.
53
-------
Figure 59. Site M-ll; Impactor Stage 7; June 11; Nuclepore substrate; Large
upper right crystal is ammonium sulfate; SEI; 300x.
'?:!'* -r *»* -S&Pvv*>- '-"' ^/-' * - '- ₯'»"iT
Figure 60. Site M-14; Hi-vol; June 11; SUP; 163x.
54
-------
m* ra**- 1
f*':jfr'*~
vt^*-r-.y:it:'-.r^-S?>
Figure 61. Same sample as Figure 60; SUP; 407x.
Figure 62. Site M-14; Impactor Stage 0; June 11; Nuclepore substrate; Cubi-
cal particle is NaCl; Amorphous particle is calcium (carbonate);
SEI; 3000x.
55
-------
riiiiiiiiiiiiiiiiimi
iiiiiiimiiiimmiiiiinnii
llinilllllllllllllllllHHHH
Figure 63. Site M-14; Impactor Stage 3; June 11; X-ray spectrum of whole
sample; Peaks present are Na, Mg, Al, Si, S, Cl, K, Ca, Ti, and
Fe.
Figure 64.
Site M-14; Impactor Stage 3; June 11; Nuclepore substrate; SEI;
3000x.
56
-------
Figure 65. Site M-14; Impactor Stage 7; June 11; Nuclepore substrate; SEI;
300x.
57
-------
REFERENCES
Flesch, J.P., C.H. Norris, and A.E. Nugent. 1967. Calibrating Particulate
Air Samplers with Monodispersed Aerosols: Application to the Andersen Cas-
cade Impactor. Am. Ind. Hug. Assoc. J., 28:507-516.
Hardy, K.A. In press. Aerosol Source Characterization Study in Miami, Florida:
Trace Element Analysis. U. S. Environmental Protection Agency, Research
Triangle Park, North Carolina.
Johansson, T.B., R. Akselsson, and S.A.E. Johansson. 1972. Proton Induced
X-ray Emission Spectroscopy in Elemental Trace Analysis. Adv. X-ray Anal.,
15:373-387.
58
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 REPORT NO.
EPA-600/3-79-097
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
AEROSOL SOURCE CHARACTERIZATION STUDY IN MIAMI, FLORIDA
Microscopical Analysis
5. REPORT DATE
September 1979
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
R.G. Draftz
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
IIT Research Institute
10 West 35th Street
Chicago, Illinois 60616
10. PROGRAM ELEMENT NO.
1AA603 AH-05 (FY-77)
11. CONTRACT/GRANT NO.
R803078
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Sciences Research Laboratory - RTF, NC
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
6/75 - 8/77
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
In June 1975 the U.S. Environmental Protection Agency conducted an experimental
program in the Miami metropolitan area to collect atmospheric aerosols for the purpose
of identifying aerosol composition and determining aerosol sources. Samples were
collected for mass, trace metals, and microscopical analyses. Microscopical analyses
showed that the composition of Miami's TSP (total suspended particulate) was similar
to that of Chicago, St. Louis, and Philadelphia, with the exception that Miami
receives a significant impact from ocean spray. Mineral fragments resuspended by
traffic appear to be the primary aerosol mass contributor. Rubber tire fragments
and carbonaceous vehicle exhaust are also major TSP contributors. These conclusions
are based solely on three sampling days at three sites and should be confirmed by
additional studies. However, the aerosol types and amounts found in Miami are likely
to remain fairly constant throughout the year.
17,
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COS AT I Field/Group
*Air pollution
*Aerosols
*Microscopy
Weight (mass)
Miami, FL
13B
07D
14B
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
69
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
59
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